The primary stages of the charge carrier photogeneration in C60 films studied by the 100-fs laser pulse pump-probe method

The primary stages of photoinduced processes are studied in thin C₆₀ films by the femtosecond laser pump-probe method. The films were excited by 100-fs laser pulses with photon energies above (wavelengths 345 and 367 nm) and below (645 nm) the mobility threshold, the fraction of excited molecules being no more than several percent. Upon probing in the spectral range from 400 to 1100 nm, several regions with substantially different decay kinetics were observed in the difference spectrum, which is caused by the simultaneous presence of several relaxing components. The appearance of the 465-and 500-nm bleaching bands in the difference spectrum upon excitation by photons with energies both above and below the mobility threshold, which are typical for electroabsorption spectra, suggests that charge carriers are produced in both these cases. The observed dependence of relaxation on the oxygen amount in the sample volume suggests that during excitation both charged (electrons and holes) and neutral (excited molecules) components are produced. The fraction of charged components is greater upon excitation into the fundamental band. The appearance of the 500-nm absorption band delayed by 10^?13–10^?14 s, the delay being increased in the presence of oxygen, was attributed to the formation of excited anions due to the capture of electrons by C₆₀ molecules. It is concluded that upon excitation of the films by photons with the energy below the mobility threshold, charge carriers are produced due to two-photon absorption rather than due to singlet-singlet annihilation. When the films are excited by photons above the mobility threshold, the primary charge carriers are produced by direct optical excitation.     

The slowing-down of ultrafast relaxation in C60 films at high femtosecond pump intensities

60 thin film was investigated in the energy range between 1.6 eV and 3.4 eV by a pump-supercontinuum probe (PSCP) technique with a 40 fs time resolution. The relaxation rate showed pronounced spectral dependence, with a maximum at 2 eV in the region of photo-induced darkening and at 2.4 eV in the region of photo-induced bleaching. The ultrafast relaxation rate decreased with increasing pump-pulse intensity. We suggest that the observed decrease results from extraheating of the carriers in the h_u and t_1u bands due to internal conversion from higher excited states, which are populated by two-step photon absorption of the intense pump pulse. Received: 2 May 1997/Revised version: 4 August 1997     

Excited state absorption of 1,3,3,1′,3′,3′-hexamethylindotricarbocyanine Iodide: A quantitative study by ultrafast absorption spectroscopy

A quantitative investigation of HITC dissolved in methanol has been made using the method of ultrafast absorption spectroscopy with a streak camera. Samples were excited by picosecond pulses of a mode-locked ruby laser. Analysis of time-resolved spectra yielded non-exponential decay kinetics consisting of a fast (τ variable) and a slow (τ=1.13±0.08 ns) component. The excited state absorption spectrum has its maximum at 493 nm and shoulders at 415 and 540 nm. The excited state absorption cross section was determined by simulataneous measurement of the bleaching of ground state absorption taking polarization of excitation and probe light and excited state absorption at the laser wavelength into account. A value of σ₁ (493 nm)=1.0·10^?16 cm² was found.     

Femtosecond dynamics of primary processes in visual pigment rhodopsin

The dynamics of the coherent photoisomerization of the 11-cis-retinal in bovine rhodopsin is studied by femtosecond time-resolved laser absorption spectroscopy with a resolution of 30 fs. Rhodopsin is excited with 500-, 535-, and 560-nm femtosecond pulses to produce different initial Franck-Condon states with different vibrational energies of the molecule in its electronically excited state. The time evolution of the photoinduced differential absorption spectra of rhodopsin is measured upon excitation with a femtosecond pulse in a spectral range from 400 to 720 nm. Oscillations in the time-resolved absorption of the rhodopsin photoproducts, such as photorhodopsin with a vibrationally excited all-trans-retinal and in its initial-state rhodopsin with a vibrationally excited 11-cis-retinal, are examined. It is demonstrated that these oscillations reflect the dynamics of coherent vibrational wavepackets. The Fourier transform of these oscillatory components yields frequencies, amplitudes, and initial phases of various vibrational modes involved in the motion the wavepackets in both photoproducts. The main vibrational modes manifest themselves at frequencies of 62 and 160 cm^?1 for photorhodopsin and 44 and 142 cm^?1 for initial-state rhodopsin. It is shown that these vibrational modes are directly involved in the coherent reaction under the study, with their amplitudes in the power spectrum produced by the Fourier transform of the kinetic curves being dependent on the wavelength of rhodopsin excitation.     

Anti-stokes emission in an additively colored KCl caused by excitation with a Nd: YAG laser

Abstract

We have observed the quadratic laser power dependence of two anti-Stokes emission bands at 15100cm^?1 and 14000cm^?1 in an additively colored KCl when excited with a Nd:YAG laser. The cross section of two photon absorption to cause the 14000cm^?1 band is estimated to be 4×10^?40cm⁴sec. We have observed that emission intensities are dependent on temperature in the range between 4. 2K and 130K. They are enhanced by means of optical bleaching and also with the increase of the F concentration. From a qualitative analysis of these observations, we propose that these emissions are correlated to the loose aggregation of the F centers.     

Observation of coherent phonon states in porous silicon films

The dynamics of differential transmission and reflectance spectra of porous silicon films was studied using the femtosecond excitation technique (τ≈50 fs, ?ω_pump=2.34 eV) with supercontinuum probing (?ω_probe=1.6–3.2 eV) and controlled time delay with a step of Δt=7 fs between the pump and probe pulses. A short-lived region of photoinduced bleaching was observed in the differential transmission spectra at wavelengths shorter than the pump wavelength. The excitation of coherent phonon states with a spectrum corresponding to nanocrystalline silicon with an admixture of a disordered phase was observed. The relaxation of electronic excitation was found to slow down in the spectral region where the amplitude of excited coherent vibrations was maximal.     

Laser excited luminescence spectra of zirconia

Luminescence spectra of ivory zirconia (Zr0₂) excited by an argon-ion laser (19,436–21,839 cm^?1) reveal a complex pattern consisting of both sharp and diffuse peaks in the 16,000–19,000 cm^?1 region. The intensity behavior of these features depends markedly on the excitation frequency. The sharp luminescence peaks of the 18,140–18,600 cm^?1 region are attributed to phonon-mediated de-excitation of excited states of the impuriity-doped ZrO₂ lattice. The more diffuse luminescence bands of the 17,700–18,000cm^?1 region may be associated with the electron traps observed in glow experiments and/or with higher-order phonon processes.     

Picosecond spectroscopy of dye solutions

Using picosecond spectroscopy technique the rotational relaxation time of rhodamine 4C in solutions both in the ground and excited states is measured to be the same and equal to 250 ps.

While anti-Stokes exciting of non-substituted rhodamine ethanol solution by a single 530 nm picosecond pulse, the blue shift of the gain spectrum on 6 nm over 350 ps after excitation was observed, the process being explained by the orientational solvate relaxation.     

Ultra-fast optical spectroscopy of micelle-suspended single-walled carbon nanotubes

We present results of wavelength-dependent ultra-fast pump–probe experiments on micelle-suspended single-walled carbon nanotubes. The linear absorption and photoluminescence spectra of the samples show a number of chirality-dependent peaks and, consequently, the pump–probe results sensitively depend on the wavelength. In the wavelength range corresponding to the second van Hove singularities (VHSs) we observe subpicosecond decays, as has been seen in previous pump–probe studies. We ascribe these ultra-fast decays to intraband carrier relaxation. On the other hand, in the wavelength range corresponding to the first VHSs, we observe two distinct regimes in ultra-fast carrier relaxation: fast (0.3–1.2 ps) and slow (5–20 ps). The slow component, which has not been observed previously, is resonantly enhanced whenever the pump photon energy resonates with an interband absorption peak, and we attribute it to interband carrier recombination. Finally, the slow component is dependent on the pH of the solution, which suggests an important role played by H⁺ ions surrounding the nanotubes. PACS 78.47.+p; 78.67.Ch; 73.22.-f     

Femtosecond time-resolved difference absorption spectroscopy of all-trans-β-Apo-8′-carotenal

The femtosecond time-resolved difference absorption spectra of all-trans-βApo-8′-carotenal have been recorded and analyzed by the singular-value decomposition (SVD) method followed by global fitting using a sequential model for the excited-state energy relaxation. With this model, we have obtained the excited-state absorption spectra and the lifetimes of the corresponding excited states both in nonpolar solvent n-hexane and polar solvent methanol. Three excited states, namely S3(170fs), S2(2.32ps) and S1(26ps) in n-hexane, and two excited states S2 (190fs) and S1(9.4ps) in methanol have been observed. The excited-state absorption spectra of all-trans-β-Apo-8′-carotenal in methanol display a red shift and broadeness, while the lifetime of S1 state becomes shorter. It is proposed that these effects are related to the presence of a carbonyl functional group that leads to the solvent effect on the excited-state energy level. At the same time, it is shown that the SVD method is a useful tool in resolving the time-resolved absorption spectra.     

Neutron-induced molecular defect O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> in beryllium orthogermanate

Be₂GeO₄ polycrystalline samples preliminarily irradiated by fast neutrons (E ～ 1 MeV, Φ = 4.5 × 10¹⁷ cm^?2) were studied by photoluminescence spectroscopy using synchrotron radiation pulses for excitation. The neutron-induced luminescence band observed at 1.7 eV in the spectra of the irradiated samples is assigned to the radiative relaxation of a molecular ion O ₂ ^? . The luminescence of these defects in the Be₂GeO₄ structure is effectively excited by 4.7-and 5.2-eV photons. At low temperatures (10 K), the profiles of the photoluminescence and excitation bands have a fine structure characteristic of electron-vibration interactions. The vibration frequencies for the ground state (v₁ = 161 cm^?1) and two excited states (v₂ = 672 cm^?1 and v₃ = 887?1451 cm^?1) were measured. Potential curves of the energy states of the O ₂ ^? center are constructed in terms of the Morse model using the experimental data. The optical spectrum fine structure is shown to be predominantly due to intrinsic vibrations of the molecular defect.     

Orientational relaxation of pheophorbide-a molecules in the ground and in the first excited state measured by transient dichroism spectroscopy

We report on transient dichroism spectroscopy carried out on pheophorbide-a in ethanol to measure the response time of the pump-beam induced anisotropy after selective excitation at high excitation levels. From the observed time behaviors of induced absorption, transient amplification, and of the bleaching signal, the orientational relaxation times of pheophorbide-a in the first excited singlet state and in the ground state were obtained separately to be 370 and 250 ps, respectively. It is found that pheophorbide-a behaves like a spherical rotor in the first excited state, while in the ground state randomization of molecules is dominated by the rotation around its quasi-symmetry axis. Because of rotation free measurement of ordinary transient absorption spectra fail in the case of ground state depletion, the observed orientational relaxation time of the ground state have to be taken into account to fit the bleaching kinetics obtained from transient absorption spectra very well to determine the intersystem crossing yield of pheophorbide-a to be 0.46.     

Dynamic quenching of the dual fluorescence of molecules

Mathematical relations describing the properties of spontaneous steady-state dual fluorescence under conditions of dynamic quenching of excited states by foreign impurities are derived. It is shown that, in the case of a kinetic character of the reaction, the initial form of the dye and its photoproduct are quenched, the intensity ratio of the fluorescence bands of the initial form and the product linearly increasing with the quencher concentration. Analysis performed is applicable to a wide range of photoreactions accompanied by the dual fluorescence (charge transfer, proton transfer, complexation, etc.). The properties of the fluorescence, absorption, and dual fluorescence excitation for 3-hydroxyflavone in acetonitrile under conditions of dynamic quenching by the TEMPO spin quencher with a concentration below 1.25 × 10^?2 M are studied. 3-Hydroxyflavone is characterized by the excited-state intramolecular proton transfer and by the fluorescence spectrum consisting of two well-spaced bands. The observed dependences of the intensity of both fluorescence bands on the quencher concentration correspond to the theoretical conclusions. The Stern-Volmer constants calculated from the experimental data on the assumption of diffusion quenching of the excited states are 858 and 1141 M^?1 for the normal and tautomeric fluorescence bands, respectively. The experimental results reveal the kinetic character of the excited-state proton transfer in 3-hydroxyflavone in acetonitrile.     

UV excitation spectra of thermoluminescence in quartz

Thermoluminescence was excited at 300 K in natural quartz crystals by monochromatic ultraviolet radiation. The excitation spectra of the main glow peaks were measured in the spectral region 1150–2000 Å. A strong excitation maximum appeared for all measured glow peaks in the region of high absorbance on the long wavelength tail of a sharp reflectance peak at 1275 Å. Some glow peaks showed excitation maxima also at photon energies smaller than the absorption edge of the material. The dependence of the TL intensities on the dose of the exciting radiation was investigated for various glow peaks and excitation wavelengths. A sublinear dependence was recorded for some peaks by excitation at 1275 Å, while the same peaks showed a strictly linear dependence up to relatively high radiation doses, when excited at 1600 Å.     

Electron-hole plasma in pulse photoexcited single quantum wells

We report photoluminescence studies of MOCVD grown, GaAsAl_xGa_1?xAs single quantum wells which were intensly excited with a pulse dye laser at T=2K. For a well width of d～40Å, the spectra are interpreted as due to the radiative recombination of a hot electron-hole plasma confined to the well. The density of charge carriers and their temperature depend upon the excitation intensity, and vary in the range of 10¹¹–10¹³ cm^?2 and 100–500K for an absorbed photon flux of 10¹³–10¹⁶ photons-cm^?2 per pulse, respectively. The observed spectral features are identified as the e1-hh1 and e1-lh1 transitions and two additional bands which are tentatively assigned to transitions involving virtual bound states of either the electron or the hole. The electron-hole plasma spectra of the d～40Å sample are strongly polarized perpendicular to the well quantization axis. For wider wells (d～80 and 150Å) smaller photoexcited carrier densities were observed for the same absorbed photon flux. It is thus concluded that the capture efficiency of the well is small.     

Formation of transient pairs of F and H centers at next nearest neighbor sites in alkali chloride crystals studied by the time delayed double excitation spectroscopy in picosecond range

Abstract

By making use of the time delayed double excitation spectroscopy, transient absorption spectra just after the excitation of self-trapped excitons (STE) from the lowest triplet state to higher excited states have been observed to find the transient F-H center pair [F-H]. Absorption bands due to transient [F-H] appeared as a doublet peaking at 2.70eV and 2.86eV (NaCl), at 2.25eV and 2.38eV (KCl) and at 1.97eV and 2.09eV (RbCl) at 108ps after the excitation. The ratio of peak heights between bands at low and high energy sides was 2:1 in all crystals. The results were tentatively understood by a recent theory for the STE by Song et al. (1987).     

Spectral broadening and kinetic properties of a Dapoxyl fluorescent probe

The steady-state spectra of Dapoxyl in polar solutions under selective excitation demonstrate considerable spectral inhomogeneity (about 600 cm^?1) in the case of a high viscosity solution. The time characteristics of the luminescence decay in different spectral regions and a long-wavelength shift of the instantaneous emission spectra indicate the occurrence of relaxation processes leading to a decrease in the excited-state energy. A correlation between the luminescence spectra and the processes of intermolecular orientational relaxation of the solution is established.     

Interband recombination dynamics in resonantly excited single-walled carbon nanotubes

Wavelength-dependent pump-probe spectroscopy of micelle-suspended single-walled carbon nanotubes reveals two-component dynamics. The slow component (5-20 ps), which has not been observed previously, is resonantly enhanced whenever the pump photon energy coincides with an absorption peak and we attribute it to interband carrier recombination, whereas we interpret the always-present fast component (0.3-1.2 ps) as intraband carrier relaxation in nonresonantly excited nanotubes. The slow component decreases drastically with decreasing pH (or increasing H+ doping), especially in large-diameter tubes. This can be explained as a consequence of the disappearance of absorption peaks at high doping due to the entrance of the Fermi energy into the valence band, i.e., a 1D manifestation of the Burstein-Moss effect.     

Femtosecond time-resolved difference absorption spectroscopy of all-<Emphasis Type="Italic">trans</Emphasis>-β-Apo-8′-carotenal

The femtosecond time-resolved difference absorption spectra of all-trans-β-Apo-8′-carotenal have been recorded and analyzed by the singular-value decomposition (SVD) method followed by global fitting using a sequential model for the excited-state energy relaxation. With this model, we have obtained the excited-state absorption spectra and the lifetimes of the corresponding excited states both in nonpolar solvent n-hexane and polar solvent methanol. Three excited states, namely S₃(170fs), S₂(2.32ps) and S₁(26ps) in n-hexane, and two excited states S₂(190fs) and S₁(9.4ps) in methanol have been observed. The excited-state absorption spectra of all-trans-β-Apo-8′-carotenal in methanol display a red shift and broadeness, while the lifetime of S₁ state becomes shorter. It is proposed that these effects are related to the presence of a carbonyl functional group that leads to the solvent effect on the excited-state energy level. At the same time, it is shown that the SVD method is a useful tool in resolving the time-resolved absorption spectra.     

Computer Resolution and Franck-Condon Analysis of the Electronic Absorption Spectrum of KMnO4 in Water

Abstract

The electronic absorptíon spectrum of KMnO₄ in water solution was analyzed. The spectral contour was resolved into component bands and then Franck-Condon approach was applied. In the investigated range of 13000–48000 cm^?1 a presence of three structureless and of two vibronic strong bands was stated. The change in the Mn-O equilibrium bond length was found to be 10.5pm for 2e·1t₁ transition (vibronic band about 18000cm^?1) and to be 16pm for the 2e·3t₂ transition (vibronic band about. 30000cm_?1). The appropriate wavenumber of the vibrational mode in these excited electronic states was found to be 735cm^?1 and about 780cm^?1, respectively. The ground electronic state wavenumber of the totally symmetric vibrational mode was fitted to be equal to 828cm^?1. Details of the proposed method of computer elaboration of electronic spectra with vibrational structure were discussed.

Electronic absorption spectra of some inorganic comppunds consist of a number of strongly overlapped bands due to their vibronic structure.^1–5 A detailed analysis of spectral contours of such compounds provides some useful information about their structure in both ground excited electronic states.

The electronic spectrum of permanganate ion is the typical example of vibronic spectra.¹ The main part of the past works based on the analysis of permanganate ion spectra in low temperatures and different polarizations. In such conditions the vibronic structure is rather good resolved and can be effectively studies.^1,3,6 Spectra of solutions as a rule are relatively poor resolved so their analysis has to be more sophisticated.

The main purpose of this work is a presentation of a new computer method for an effective study of vibronic spectra of solutions. This method has been applied to the electronic absorption spectrum of KMnO₄ in water. The method allowed us to fit the geometric parameters of spectral contour, to establish the origins and parameters of two progressions in the UV/VIS range as well as to calculate the changes in the Mn-0 equilibrium bond lengths and vibrational energy resulting from the electronic excitations of the soluted permanganate ion.